U.S. patent application number 12/289455 was filed with the patent office on 2009-04-30 for resin composition, prepreg and laminate using the same.
This patent application is currently assigned to MITSUBISHI GAS CHEMICAL COMPANY, INC.. Invention is credited to Hironao Fukuoka, Masayuki Katagiri, Yoshimasa Nishimura, Masanobu Sogame, Yuuichi Sugano.
Application Number | 20090110938 12/289455 |
Document ID | / |
Family ID | 40260506 |
Filed Date | 2009-04-30 |
United States Patent
Application |
20090110938 |
Kind Code |
A1 |
Nishimura; Yoshimasa ; et
al. |
April 30, 2009 |
Resin composition, prepreg and laminate using the same
Abstract
A cyanate ester resin composition for a printed wiring board
material containing a cyanate ester resin component A comprising a
cyanate ester compound represented by the formula (1) and/or an
oligomer thereof, and at least one component B selected from the
group consisting of an epoxy resin and a maleimide compound, which
resin composition is improved in heat resistance and heat
resistance after moisture absorption, is excellent in mechanical
properties such as elastic modulus and has flame retardancy without
a halogen compound, and ##STR00001## a prepreg and a laminate each
of which uses the resin composition defined as above wherein the
resin composition contains the component A and at least the epoxy
resin as the component B.
Inventors: |
Nishimura; Yoshimasa;
(Niigata-shi, JP) ; Sogame; Masanobu; (Tokyo,
JP) ; Fukuoka; Hironao; (Tokyo, JP) ; Sugano;
Yuuichi; (Niigata-shi, JP) ; Katagiri; Masayuki;
(Niigata-shi, JP) |
Correspondence
Address: |
WENDEROTH, LIND & PONACK, L.L.P.
1030 15th Street, N.W.,, Suite 400 East
Washington
DC
20005-1503
US
|
Assignee: |
MITSUBISHI GAS CHEMICAL COMPANY,
INC.
|
Family ID: |
40260506 |
Appl. No.: |
12/289455 |
Filed: |
October 28, 2008 |
Current U.S.
Class: |
428/425.8 ;
524/538; 525/450 |
Current CPC
Class: |
B32B 2260/046 20130101;
B32B 15/14 20130101; B32B 2262/0261 20130101; B32B 2307/51
20130101; C08G 59/4014 20130101; C08L 63/00 20130101; Y10T
428/31605 20150401; B32B 27/16 20130101; B32B 2307/546 20130101;
B32B 27/34 20130101; B32B 2262/106 20130101; B32B 2307/306
20130101; B32B 5/026 20130101; B32B 27/36 20130101; C08G 73/0655
20130101; B32B 5/26 20130101; B32B 2262/02 20130101; C08G 73/16
20130101; B32B 2262/14 20130101; B32B 2307/714 20130101; B32B 5/022
20130101; B32B 5/024 20130101; B32B 27/281 20130101; B32B 2262/108
20130101; B32B 2262/062 20130101; B32B 2260/021 20130101; B32B
15/20 20130101; B32B 2307/50 20130101; H05K 1/0353 20130101; B32B
5/028 20130101; B32B 2262/10 20130101; B32B 2307/3065 20130101;
B32B 2307/204 20130101; B32B 27/08 20130101; B32B 2457/08 20130101;
B32B 2262/101 20130101 |
Class at
Publication: |
428/425.8 ;
525/450; 524/538 |
International
Class: |
B32B 27/36 20060101
B32B027/36; C08L 79/00 20060101 C08L079/00; C08L 63/00 20060101
C08L063/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 29, 2007 |
JP |
280266/2007 |
Oct 30, 2007 |
JP |
281217/2007 |
Oct 30, 2007 |
JP |
281218/2007 |
Claims
1. A resin composition containing a cyanate ester resin component A
comprising a cyanate ester compound represented by the formula (1)
and/or an oligomer thereof, and at least one component B selected
from the group consisting of an epoxy resin and a maleimide
compound. ##STR00003##
2. The resin composition according to claim 1, which further
contains an inorganic filler.
3. The resin composition according to claim 1, wherein the
component B comprises the epoxy resin or the epoxy resin and the
maleimide compound.
4. The resin composition according to claim 3, wherein the epoxy
resin is a non-halogen epoxy resin.
5. A cured product obtained by curing the resin composition as
defined in claim 1.
6. A prepreg comprising the resin composition as defined in claim 3
and a base material.
7. A laminate obtained by curing the prepreg as defined in claim
6.
8. A metal-foil-clad laminate obtained by laminating the prepreg as
defined in claim 6 and a metal foil and curing the prepreg with the
metal foil.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a resin composition
suitably used for a printed wiring board where an electric circuit
is to be formed, and a prepreg and a laminate each of which uses
the above resin composition.
BACKGROUND OF THE INVENTION
[0002] A cyanate ester resin has been known as a thermosetting
resin excellent in heat resistance after moisture absorption and
dielectric characteristics. A resin composition containing a
bisphenol A type cyanate ester resin and other thermosetting resin
or thermoplastic resin has been disclosed (for example,
JP-B2-54-30440). Such resin compositions have excellent properties
in terms of electric properties, mechanical properties, chemical
resistance and adhesive properties. Therefore, on the basis of
these technologies, such resin compositions are widely used for
materials for high-function printed wiring boards for use in
semiconductor plastic packages in recent years. However, the
bisphenol A type cyanate ester resin is insufficient in heat
resistance under severe conditions in some cases so that studies on
cyanate ester resins having other structures have been conducted.
Moreover, in accordance with a recent demand for reduction in size
and weight of electric parts, further improvements of a resin
composition as a raw material are demanded in mechanical properties
such as heat resistance or elastic modulus.
[0003] Further, flame retardancy is generally necessary to a resin
composition for printed wiring boards. Generally, a bromine flame
retardant is jointly incorporated (for example, JP-A-11-021452).
However, a resin composition containing no halogen compound is
desired in accordance with a recent growing interest in
environmental issues. In addition, with regard to the bisphenol A
type cyanate ester resin, it is required that an inorganic filling
material in an amount larger than normal is incorporated for
satisfying the requirement of flame retardancy. Through the
influence thereof, there is a problem about moldability and a
limitation is imposed on an improvement in the appearance of a
substrate.
[0004] For overcoming these problems, resin compositions based on
the cyanate ester resins having other structures have been studied.
A novolak type cyanate ester resin is broadly known as a cyanate
ester resin excellent in heat resistance and flame retardancy (for
example, JP-A-11-124433). However, the novolak type cyanate ester
resin is apt to be insufficient in curing degree under normal
curing conditions. A cured product obtained therefrom has a large
water absorption coefficient and decreases in heat resistance after
moisture absorption. As means for improving the novolak type
cyanate ester resin, a co-prepolymer thereof with a bisphenol A
type cyanate ester resin is disclosed (for example,
JP-A-2000-191776). Although the above co-prepolymer is improved in
curability, it is still insufficient in terms of improvements in
properties. Therefore, there is a strong demand for a cyanate ester
resin composition which not only has heat resistance and heat
resistance after moisture absorption but also secures flame
retardancy without the use of a halogenous flame retardant.
SUMMARY OF THE INVENTION
[0005] It is an object of the present invention to provide a
cyanate ester resin composition for a printed wiring board material
which composition is improved in heat resistance and heat
resistance after moisture absorption, is excellent in mechanical
properties such as elastic modulus and has flame retardancy without
a halogen compound and to provide a prepreg and a laminate each of
which uses the above resin composition.
[0006] The present inventors have found that a resin composition
having high curability, excellent heat resistance and excellent
heat resistance after moisture absorption can be obtained by
incorporating an epoxy resin into a cyanate ester resin having a
specific structure. In particular, the present inventors have found
that the incorporation of a non-halogen epoxy resin and an
inorganic filler gives a halogen-free resin composition having
flame retardancy. Further, the present inventors have found that a
thermosetting resin composition excellent in heat resistance and
elastic modulus can be obtained by jointly incorporating a
maleimide compound into the cyanate ester resin having a specific
structure. On the basis of these findings, the present inventors
have completed the present invention.
[0007] The present invention provides a resin composition
containing a cyanate ester resin component A comprising a cyanate
ester compound represented by the formula (1) and/or an oligomer
thereof, and at least one component B selected from the group
consisting of an epoxy resin and a maleimide compound.
##STR00002##
[0008] The present invention further provides a resin composition
according to the above which further contains an inorganic filler
and a cured product obtained by curing the above resin
composition.
[0009] The present invention furthermore provides a resin
composition containing a cyanate ester resin component A comprising
a cyanate ester compound represented by the above formula (1)
and/or an oligomer thereof, and a component B comprising an epoxy
resin or an epoxy resin and a maleimide compound. The present
invention still further provides a resin composition according to
the above which further contains an inorganic filler, a resin
composition according to the above wherein the epoxy resin is a
non-halogen epoxy resin, a prepreg comprising the above resin
composition and a base material, a laminate comprising the above
prepreg and a metal-foil-clad laminate obtained by using the above
prepreg.
EFFECT OF THE INVENTION
[0010] The resin composition provided by the present invention is
excellent in heat resistance and flame retardancy owing to the
stiff skeleton structure of the specific cyanate ester resin. In
addition, the resin composition of the present invention is
increased in curability since the incorporation of the epoxy resin
and/or the bismaleimide compound reduces reaction inhibition
factors which are based on the molecular structure, etc., of
cyanate ester resin. Accordingly, the resin composition of the
present invention has excellent heat resistance after moisture
absorption and high elastic modulus. Further, the laminate or the
metal-foil-clad laminate obtained by curing the prepreg of the
present invention is suitable for a high-density-support printed
wiring board material. The industrial practicality of the present
invention is remarkably high.
DETAILED DESCRIPTION OF THE INVENTION
[0011] The component A used in the present invention refers to a
cyanate ester resin comprising a cyanate ester compound represented
by the formula (1) and/or an oligomer thereof. The cyanate ester
compound represented by the formula (1) is obtained by condensation
of 3,3-bis(4-hydroxyphenyl)-1(3H)-isobenzofuranone and a cyanic
acid. The method of producing the cyanate ester compound
represented by the formula (1) is not specially limited. Any known
cyanate ester synthesis method can be employed for its production.
Specifically, for example, it is obtained by reacting
3,3-bis(4-hydroxyphenyl)-1(3H)-isobenzofuranone and a cyanogen
halide in an inactive organic solvent in the presence of a basic
compound. The oligomer of the cyanate ester compound represented by
the formula (1) can be, for example, obtained by melting the
cyanate ester compound of the formula (1) at a temperature of from
140 to 160.degree. C. and reacting cyanate ester groups with
stirring.
[0012] The component B used in the present invention refers to a
compound which comprises an epoxy resin and/or a maleimide compound
and can be reacted with cyanate ester groups.
[0013] The epoxy resin used as the component B is not specially
limited so long as it is a compound having at least two epoxy
groups. Examples thereof include a bisphenol A type epoxy resin, a
bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a
cresol novolak type epoxy resin, a bisphenol A novolak type epoxy
resin, a brominated bisphenol A type epoxy resin, a brominated
phenol novolak type epoxy resin, a trifunctional phenol type epoxy
resin, a tetrafunctional phenol type epoxy resin, a naphthalene
type epoxy resin, a biphenyl type epoxy resin, a phenol aralkyl
type epoxy resin, a biphenyl aralkyl type epoxy resin, a naphthol
aralkyl type epoxy resin, an alicyclic epoxy resin, a polyol type
epoxy resin, a phosphorus-containing epoxy resin, glycidyl amine,
glycidyl ester, a compound obtained by epoxidation of a double bond
of butadiene or the like, and a compound obtained by a reaction of
a hydroxyl-group-containing silicon resin with epichlorohydrin. The
above epoxy resin is preferably a bisphenol A type epoxy resin, a
bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a
cresol novolak type epoxy resin, a bisphenol A novolak type epoxy
resin, a brominated bisphenol A type epoxy resin, a brominated
phenol novolak type epoxy resin, a biphenyl type epoxy resin, a
phenol aralkyl type epoxy resin, a biphenyl aralkyl type epoxy
resin or a naphthol aralkyl type epoxy resin. The epoxy resin can
be used alone or at least two epoxy resins can be used in
combination as required.
[0014] Further, the resin composition can become a halogen-free
resin composition by using as the epoxy resin a non-halogen epoxy
resin which intentionally does not have a halogen atom in a
molecule. The non-halogen epoxy resin is not specially limited.
Examples thereof include a bisphenol A type epoxy resin, a
bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a
cresol novolak type epoxy resin, a bisphenol A novolak type epoxy
resin, a trifunctional phenol type epoxy resin, a tetrafunctional
phenol type epoxy resin, a naphthalene type epoxy resin, a biphenyl
type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl
aralkyl type epoxy resin, a naphthol aralkyl type epoxy resin, an
alicyclic epoxy resin, a polyol type epoxy resin, a
phosphorus-containing epoxy resin, glycidyl amine, glycidyl ester,
a compound obtained by epoxidation of a double bond of butadiene or
the like, and a compound obtained by a reaction of a
hydroxyl-group-containing silicon resin with epichlorohydrin. The
above non-halogen epoxy resin is preferably a phenol novolak type
epoxy resin, a biphenyl type epoxy resin, a phenol aralkyl type
epoxy resin, a biphenyl aralkyl type epoxy resin or a naphthol
aralkyl type epoxy resin. The non-halogen epoxy resin can be used
alone or at least two non-halogen epoxy resins can be used in
combination as required.
[0015] When the epoxy resin is used as the component B, the mixing
ratio between the component A and the epoxy resin is not specially
limited. The weight ratio of component A epoxy resin is preferably
in the range of from 10:90 to 90:10, particularly preferably from
30:70 to 70:30. When the non-halogen epoxy resin is used as the
epoxy resin, the above weight ratio range is also preferred. When
the amount of the component A is too small, a laminate obtained
decreases in heat resistance. When it is too large, solvent
solubility or curability decreases.
[0016] The maleimide compound used as the component B is not
specially limited so long as it is a compound having at least two
maleimide groups in a molecule. Specific examples thereof include
bis(4-maleimidophenyl)methane,
2,2-bis{4-(4-maleimidophenoxy)phenyl}propane,
bis(3,5-dimethyl-4-maleimidophenyl)methane,
bis(3-ethyl-5-methyl-4-maleimidophenyl)methane,
bis(3,5-diethyl-4-maleimidophenyl)methane, polyphenyl methane
maleimide, prepolymers of these maleimide compounds, and a
prepolymer of one of these maleimide compounds and an amine
compound. The maleimide compound can be used alone or at least two
maleimide compounds can be used in combination as required. The
maleimide compound is more preferably
bis(4-maleimidophenyl)methane,
2,2-bis{4-(4-maleimidophenoxy)phenyl}propane or
bis(3-ethyl-5-methyl-4-maleimidophenyl)methane.
[0017] When the maleimide compound is used as the component B, the
mixing ratio between the component A and the maleimide compound is
not specially limited. The weight ratio of component A:maleimide
compound is preferably in the range of from 25:75 to 95:5,
particularly preferably from 30:70 to 90:10. When the amount of the
component A is too small, a laminate obtained decreases in
properties after moisture absorption. When it is too large, bending
strength or heat resistance is decreased.
[0018] When the epoxy resin and the maleimide compound are used in
combination as the component B, reaction inhibition factors, which
are based on the molecular structure, etc., of a cyanate ester
resin, are reduced so that the resin composition is improved in
curability and excellent effects are shown in terms of heat
resistance after moisture absorption and heat resistance.
Therefore, it is preferred to use the epoxy resin and the maleimide
compound in combination.
[0019] The inorganic filler used in the present invention is not
specially limited so long as it is selected from generally-used
inorganic fillers. Specific examples thereof include silicas such
as natural silica, fused silica, amorphous silica and hollow
silica, metal hydroxides such as aluminum hydroxide, a heat-treated
product of aluminum hydroxide (obtained by heat-treating aluminum
hydroxide and decreasing crystal water partially), boehmite and
magnesium hydroxide, molybdenum compounds such as molybdenum oxide
and zinc molybdate, zinc borate, zinc stannate, alumina, clay,
kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica,
short glass fiber (fine powders of glasses such as E glass or D
glass) and hollow glass. The average particle diameter of the
inorganic filler is 0.1 to 10 .mu.m, preferably 0.2 to 5 .mu.m. The
inorganic fillers which are different from each other in terms of
particle size distribution and/or average particle diameter can be
used in combination as required. The amount of the inorganic filler
is not specially limited. It is preferably 10 to 300 parts by
weight, particularly preferably 30 to 200, per 100 parts by weight
of the total amount of the component A and the component B.
[0020] A silane-coupling agent or a wetting and dispersing agent
can be jointly used with the above inorganic filler used in the
present invention. The silane-coupling agent is not specially
limited so long as it is selected from silane coupling agents which
are generally used for surface-treating inorganic substances.
Specific examples thereof include aminosilane coupling agents such
as .gamma.-aminopropyltriethoxysilane and
N-.beta.-(aminoethyl)-.gamma.-aminopropyltrimethoxysilane,
epoxysilane coupling agents such as
.gamma.-glycidoxypropyltrimethoxysilane, vinylsilane coupling
agents such as .gamma.-methacryloxypropyltrimethoxysilane, cationic
silane coupling agents such as
N-.beta.-(N-vinylbenzylaminoethyl)-.gamma.-aminopropyltrimethoxysilane
hydrochloride and phenylsilane coupling agents. The silane coupling
agent can be used singly or at least two silane coupling agents can
be used in combination, as required. The wetting and dispersing
agent is not specially limited so long as it is selected from
dispersion stabilizers which are used for coatings. For example,
copolymer-based wetting and dispersing agents having an acid group
such as Disperbyk-110, 111, 996 and W903 supplied by Big Chemie
Japan can be used.
[0021] A curing accelerator can be jointly incorporated into the
resin composition of the present invention, as required, for the
purpose of properly controlling the curing speed. The curing
accelerator is not specially limited so long as it is selected from
curing accelerators which are generally used for a cyanate ester
resin, an epoxy resin or a maleimide compound. Specific examples of
the curing accelerator, which is to be used when the component B is
the epoxy resin, include salts of organic metals such as copper,
zinc, cobalt and nickel, imidazoles and derivatives thereof, and
tertiary amines. Specific examples of the curing accelerator, which
is to be used when the component B is the maleimide compound,
include organic peroxides such as benzoyl peroxide, lauroyl
peroxide, acetyl peroxide, parachlorobenzoyl peroxide and
di-tert-butyl-di-perphthalate; azo compounds such as azobisnitrile;
imidazoles such as 2-methylimidazole, 2-undecylimidazole,
2-phenylimidazole, 2-ethyl-4-methylimidazole,
1-benzyl-methylimidazole, 1-cyanoethyl-2-methylimidazole,
1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-undecylimidazole,
1-cyanoethyl-2-phenylimidazole,
1-cyanoethyl-2-ethyl-methylimidazole,
1-guanaminoethyl-2-methylimidazole, carboxylic acid adducts of
these imidazoles and carboxylic anhydride adducts of these
imidazoles; tertiary amines such as N,N-dimethylbenzylamine,
N,N-dimethylaniline, N,N-dimethyltoluidine,
2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline,
N-methylmorpholine, triethanolamine, triethylenediamine,
tetramethylbutanediamine and N-methylpiperidine; phenols such as
phenol, xylenol, cresol, resorcin and catechol; organic metal salts
such as lead naphthenate, lead stearate, zinc naphthenate, zinc
octylate, tin oleate, dibutyltin maleate, manganese naphthenate,
cobalt naphthenate and acetylacetone iron; a substance obtained by
dissolving any one of these organic metal salts in a
hydroxyl-group-containing compound such as phenol or bisphenol;
inorganic metal salts such as tin chloride, zinc chloride and
aluminum chloride; and organotin compounds such as dioctyltin
oxide, other alkyltin and alkyltin oxide. The curing accelerator
may be added in an ordinary amount. For example, the amount of the
curing accelerator is 10 wt % or less, generally about 0.01 to 2 wt
%, based on the resin composition.
[0022] The resin composition of the present invention may further
contain a cyanate ester resin other than the cyanate ester compound
represented by the formula (1). The above cyanate ester resin other
than the cyanate ester compound represented by the formula (1) can
be selected from known cyanate ester resins. Example thereof
include a bisphenol A type cyanate ester resin, a bisphenol F type
cyanate ester resin, a bisphenol M type cyanate ester resin, a
bisphenol P type cyanate ester resin, a bisphenol E type cyanate
ester resin, a phenol novolak type cyanate ester resin, a cresol
novolak type cyanate ester resin, a dicyclopentadiene novolak type
cyanate ester resin, a tetramethyl bisphenol F type cyanate ester
resin, a biphenol type cyanate ester resin, a phenol aralkyl type
cyanate ester resin, a xylenol aralkyl type cyanate ester resin, a
naphthol aralkyl type cyanate ester resin and oligomers of these.
The cyanate ester resin other than the cyanate ester compound
represented by the formula (1) can be used alone or at least two
cyanate ester resins other than the cyanate ester compound
represented by the formula (1) can be used in combination, as
required.
[0023] The resin composition of the present invention can jointly
contain a variety of high polymer compounds such as a different
thermosetting resin, a thermoplastic resin and oligomers thereof,
and elastomers, a different flame retardant compound or an
additive, so long as the inherent properties of the resin
composition are not impaired. They are not specially limited so
long as they are selected from those which are generally used.
Examples of the flame retardant compound include phosphorus
compounds such as a phosphoric acid ester or a phosphoric acid
melamine, a nitrogen-containing compound such as melamine or
benzoguanamine, an oxazine-ring-containing compound and a silicone
compound. Examples of the resins include polyimide, polyvinyl
acetal, a phenoxy resin, an acrylic resin, an acrylic resin having
a hydroxyl group or a carboxylic group, an alkyd resin, a
thermoplastic polyurethane resin; elastomers such as polybutadiene,
a butadiene-acrylonitrile copolymer, polychloroprene, a
butadiene-styrene copolymer, polyisoprene, butyl rubber, fluoro
rubber and natural rubber; vinyl compound polymers such as
styrene-isoprene rubber, acrylic rubber, core shell rubbers of
these, epoxidized butadiene, maleated butadiene, polyethylene,
polypropylene, a polyethylene-propylene copolymer,
poly-4-methylpentene-1, polyvinyl chloride, polyvinylidene
chloride, polystyrene, polyvinyl toluene, polyvinyl phenol, an AS
resin, an ABS resin, an MBS resin, poly-4-fluoroethylene, a
fluoroethylene-propylene copolymer,
4-fluoroethylene-6-fluoroethylene copolymer and vinylidene
fluoride; thermoplastic resins and low-molecular-weight polymers
thereof such as polycarbonate, polyester carbonate, polyphenylene
ether, polysulfone, polyester, polyether sulfone, polyamide,
polyamide imide, polyester imide and polyphenylene sulfite;
polyallyl compounds and prepolymers thereof such as
poly(meth)acrylates, such as (meth)acrylate, epoxy(meth)acrylate
and di(meth) acryloxy-bisphenol, styrene, vinylpyrrolidone, diacryl
phthalate, divinylbenzene, diallyl benzene, diallyl ether bisphenol
and triallyl isocyanurate; and curable monomers or prepolymers such
as dicyclopentadiene and prepolymers thereof, a phenolic resin,
polymerizable-double-bond-containing monomers and prepolymers
thereof, such as an unsaturated polyester, and polyisocyanates.
Examples of the additive include an ultraviolet absorber, an
antioxidant, a photopolymerization initiator, a fluorescent
brightening agent, a photosensitizer, a dye, a pigment, a
thickener, a lubricant, an antifoamer, a dispersing agent, a
leveling agent, a brightener and a polymerization inhibitor. These
additives may be used in combination as required.
[0024] The method of mixing the resin composition containing the
component A and the component B in the present invention is not
specially limited. For example, it is possible to simply melt-blend
the component A and the component B. It is also possible to
dissolve the component A and the component B in an organic solvent
and blend them. Furthermore, the component A and the component B
can be blended after one or two selected from the component A and
the component B is/are converted into oligomer(s). Otherwise, it is
also possible to blend two or three selected from the component A
and the component B and then convert them into oligomers.
[0025] An organic solvent can be used in the resin composition of
the present invention as required. The organic solvent is not
specially limited so long as the organic solvent can dissolve a
mixture of the component A and the component B. Specific example
thereof include ketones such as such as acetone, methyl ethyl
ketone, methyl isobutyl ketone and cyclohexanone, aromatic
hydrocarbons such as benzene, toluene and xylene, amides such as
dimethylformamide and dimethylacetamide.
[0026] The resin composition of the present invention is cured
alone, whereby a cured product can be obtained. Further, the resin
composition of the present invention is impregnated into a base
material, whereby a prepreg which is applicable to a laminate or a
metal-foil-clad laminate can be obtained.
[0027] The base material suitably used in the present invention can
be selected from known base materials which are used for a variety
of printed wiring boards. Examples of the base material include
fibers of glasses such as E glass, D glass, S glass, NE glass, T
glass and quartz, inorganic fibers such as a carbon fiber, an
alumina fiber, a silicon carbide fiber, asbestos, rock wool, slag
wool and plaster whisker, and organic fibers such as polyimide,
polyamide, polyester, a fluorine fiber, a polybenzoxazole fiber,
cotton, linen and a semi-carbon fiber. The base material is
selected in accordance with an intended use or performance, as
required. The base material can be used alone or at least two base
materials can be used in combination. The form of the base material
is typically a woven fabric, a nonwoven fabric, roving, a chopped
strand mat or a surfacing mat. The thickness thereof is not
specially limited. The thickness thereof is generally approximately
0.01 to 0.3 mm. Further, a base material having been
surface-treated with a silane-coupling agent or the like and a
woven fabric having been physically opened can be preferably used
in view of heat resistance after moisture absorption. Further, a
film made of polyimide, polyamide, polyester or the like can be
used as the base material. The thickness of the film is not
specially limited. It is preferably approximately 0.002 to 0.05 mm.
A film having been surface-treated by means of plasma treatment or
the like is more preferred.
[0028] The method of producing the prepreg of the present invention
is not specially limited so long as the prepreg is produced by
combining the resin composition containing the component A and the
component B with the base material. In one example of such method,
for instance, the above resin composition is impregnated into or
applied to the base material and then the resin composition is
semi-cured by heating the resultant base material in a drying
machine at 100 to 200.degree. C. for 1 to 60 minutes or by other
procedure, thereby producing the prepreg. The content of the resin
composition, which may contain the inorganic filler, in the prepreg
is preferably 20 to 95% by weight.
[0029] The laminate and metal-foil-clad laminate provided by the
present invention are obtained by carrying out laminate-molding
using the aforesaid prepreg. Specifically, the laminate or
metal-foil-clad laminate is produced by providing one prepreg
mentioned above or stacking two or more prepregs, disposing a metal
foil such as copper or aluminum on one surface or both surfaces of
the prepreg or the stack of the prepregs, as required, and
laminate-molding the resultant set. The metal foil is not specially
limited so long as it is selected from metal foils which are
generally used as a printed wiring board material. General
technical skills for laminates and multilayer boards for printed
wiring boards can be adopted with regard to molding conditions. For
example, a multiplaten press, a multiplaten vacuum press,
continuous molding, an autoclave molding machine or the like is
generally used. The temperature is generally 100 to 300.degree. C.
The pressure is generally 2 to 100 kgf/cm.sup.2. The heating time
is generally 0.05 to 5 hours. Further, a multilayer board can be
produced by combining the prepreg of the present invention and a
wiring board, prepared separately, for an internal layer and
laminate-molding the prepreg and the wiring board.
EXAMPLES
Synthetic Example 1
Synthesis of 3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone
[0030] 2.04 mol of 3,3-bis(4-hydroxyphenyl)-1(3H)-isobenzofuranone
(supplied by Hachidai Pharmaceutical Co., LTD.) and 4.49 mol of
triethylamine were dissolved in 3,250 g of methylene chloride to
prepare a solution 1. The solution 1 was dropwise added to 1,462.45
g of a methylene chloride solution containing 5.51 mol of cyanogen
chloride dissolved therein at -10.degree. C. over 3 hours. The
mixture was stirred for 30 minutes. Then, 0.20 mol of triethylamine
was dropwise added. The mixture was further stirred for 30 minutes,
to complete the reaction. The thus-obtained solution was washed
with 3,000 mL of 0.1 N hydrochloric acid. Then, washing with 1,000
mL of water was repeated four times. The washed solution was
concentrated and then cooled to obtain a yellowish white crystal.
The crystal was washed with 2,000 mL of n-hexane and then dried
under a reduced pressure, to obtain 677 g of a white crystal of
3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone. The thus-obtained
cyanate ester compound was subjected to an infrared absorption
spectrum measurement. From the results of the measurement, it was
confirmed that the absorption of a phenolic OH group at 3,200-3600
cm.sup.-1 disappeared and an absorption was present around 2264
cm.sup.-1 corresponding to the absorption of a nitrile of cyanate
ester. The melting point was 130.degree. C.
Example 1
[0031] 70 parts by weight of
3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone obtained in
Synthetic Example 1 and 30 parts by weight of
bis(4-maleimidophenyl)methane (BMI-H, supplied by K I KASEI KK)
were melt-blended at 160.degree. C. for 10 minutes. The
melt-blended mixture was poured into a casting mold and defoamed
under vacuum at 165.degree. C. for 15 minutes. Then it was cured
under heat at 180.degree. C. for 4 hours, at 200.degree. C. for 4
hours, and at 250.degree. C. for 4 hours, thereby obtaining a cured
product having a thickness of 3 mm and a cured product having a
thickness of 2 mm. Table 1 shows the results of measurements of
physical properties of the cured products.
Comparative Example 1
[0032] A cured product having a thickness of 3 mm and a cured
product having a thickness of 2 mm were obtained in the same manner
as in Example 1 except that 70 parts by weight of
3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone used in Example 1
was replaced with 70 parts by weight of
2,2-bis(4-cyanatophenyl)propane (CX, supplied by Mitsubishi Gas
Chemical Company, Inc.). Table 1 shows the results of measurements
of physical properties of the cured products.
Comparative Example 2
[0033] A cured product having a thickness of 3 mm and a cured
product having a thickness of 2 mm were obtained in the same manner
as in Example 1 except that 70 parts by weight of
3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone used in Example 1
was replaced with 70 parts by weight of a phenol novolak type
cyanate ester resin (Primaset PT-30, supplied by LONZA). Table 1
shows the results of measurements of physical properties of the
cured products.
Comparative Example 3
[0034] 3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone obtained in
Synthetic Example 1 was molten at 160.degree. C. for 10 minutes,
then poured into a casting mold and defoamed under vacuum at
165.degree. C. for 15 minutes. Then it was cured under heat at
180.degree. C. for 4 hours, at 200.degree. C. for 4 hours, and at
250.degree. C. for 4 hours, thereby obtaining a cured product
having a thickness of 3 mm and a cured product having a thickness
of 2 mm. Table 1 shows the results of measurements of physical
properties of the cured products. In the above measurements, the
measurement of a glass transition temperature was impossible. The
glass transition temperature was uneven, probably because the
degree of curing was insufficient because of reaction inhibition
factors based on the molecular structure, etc., of cyanate ester
resin.
Example 2
[0035] 50 parts by weight of
3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone obtained in
Synthetic Example 1 and 50 parts by weight of
bis(4-maleimidophenyl)methane (BMI-H) were melt-blended at
160.degree. C. for 10 minutes. The melt-blended mixture was poured
into a casting mold and defoamed under vacuum at 165.degree. C. for
15 minutes. Then it was cured under heat at 180.degree. C. for 4
hours, at 200.degree. C. for 4 hours, and at 250.degree. C. for 4
hours, thereby obtaining a cured product having a thickness of 3 mm
and a cured product having a thickness of 2 mm. Table 2 shows the
results of measurements of physical properties of the cured
products.
Comparative Example 4
[0036] A cured product having a thickness of 3 mm and a cured
product having a thickness of 2 mm were obtained in the same manner
as in Example 2 except that 50 parts by weight of
3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone used in Example 2
was replaced with 50 parts by weight of
2,2-bis(4-cyanatophenyl)propane (CX, supplied by Mitsubishi Gas
Chemical Company, Inc.). Table 2 shows the results of measurements
of physical properties of the cured products.
Comparative Example 5
[0037] A cured product having a thickness of 3 mm and a cured
product having a thickness of 2 mm were obtained in the same manner
as in Example 2 except that 50 parts by weight of
3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone used in Example 2
was replaced with 50 parts by weight of a phenol novolak type
cyanate ester resin (Primaset PT-30, supplied by LONZA). Table 2
shows the results of measurements of physical properties of the
cured products.
TABLE-US-00001 TABLE 1 (Table 1) Comparative Comparative
Comparative Example 1 Example 1 Example 2 Example 3 Glass
transition 270 261 259 Impossible temperature (.degree. C.) to
measure Bending elastic 5.2 3.6 4.9 4.3 modulus (GPa)
TABLE-US-00002 TABLE 2 (Table 2) Comparative Comparative Example 2
Example 4 Example 5 Glass transition 273 266 251 temperature
(.degree. C.) Bending elastic 5.2 3.9 4.9 modulus (GPa)
Example 3
[0038] 45 parts by weight of
3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone obtained in
Synthetic Example 1 and 55 parts by weight of a cresol novolak type
epoxy resin (ESCN-220F, supplied by Sumitomo Chemical Co. Ltd.)
were dissolved in methyl ethyl ketone. 0.04 part by weight of zinc
octylate was mixed with the resultant solution to obtain a varnish.
The varnish was diluted with methyl ethyl ketone. The diluted
varnish was impregnated into an E glass cloth having a thickness of
0.1 mm. The impregnated varnish was dried under heat at 165.degree.
C. for 6 minutes, thereby obtaining prepregs having a resin content
of 39% by weight. Four prepregs obtained above were stacked and 18
.mu.m-thick electrolytic copper foils were placed on the upper and
lower surfaces of the stack of the prepregs, one copper foil on the
upper surface and one copper foil on the lower surface, and the
prepregs and the copper foils were pressed at a pressure of 30
kgf/cm.sup.2 at a temperature of 220.degree. C. for 120 minutes,
thereby obtaining a copper-clad laminate having a thickness of 0.4
mm. Table 3 shows the results of measurements of physical
properties of the copper-clad laminate.
Comparative Example 6
[0039] A copper-clad laminate having a thickness of 0.4 mm was
obtained in the same manner as in Example 3 except that 45 parts by
weight of 3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone used in
Example 3 was replaced with 45 parts by weight of a prepolymer of
2,2-bis(4-cyanatophenyl)propane (BT2070, supplied by Mitsubishi Gas
Chemical Company, Inc.). Table 3 shows the results of measurements
of physical properties of the copper-clad laminate.
Comparative Example 7
[0040] A copper-clad laminate having a thickness of 0.4 mm was
obtained in the same manner as in Example 3 except that 45 parts by
weight of 3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone used in
Example 3 was replaced with 45 parts by weight of a phenol novolak
type cyanate ester resin (Primaset PT-30, supplied by LONZA). Table
3 shows the results of measurements of physical properties of the
copper-clad laminate.
TABLE-US-00003 TABLE 3 (Table 3) Comparative Comparative Example 3
Example 6 Example 7 Glass transition 305 260 250 temperature
(.degree. C.) Heat resistance 0/3 0/3 2/3 after moisture absorption
Copper 0.9 0.8 0.8 foil peeling strength
Example 4
[0041] 50 parts by weight of
3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone obtained in
Synthetic Example 1 and 50 parts by weight of a biphenyl aralkyl
type epoxy resin (NC3000-H, supplied by Nippon Kayaku Co., Ltd.)
were dissolved in methyl ethyl ketone. Further, 100 parts by weight
of a spherical synthetic silica (SC-2050, supplied by ADMATECHS
CO., LTD) and 0.04 part by weight of zinc octylate was mixed with
the resultant solution to obtain a varnish. The varnish was diluted
with methyl ethyl ketone. The diluted varnish was impregnated into
an E glass cloth having a thickness of 0.1 mm. The impregnated
varnish was dried under heat at 165.degree. C. for 6 minutes,
thereby obtaining prepregs having a resin content of 45% by weight.
Four prepregs obtained above were stacked and 12 .mu.m-thick
electrolytic copper foils were placed on the upper and lower
surfaces of the stack of the prepregs, one copper foil on the upper
surface and one copper foil on the lower surface, and the prepregs
and the copper foils were pressed at a pressure of 30 kgf/cm.sup.2
at a temperature of 220.degree. C. for 120 minutes, thereby
obtaining a copper-clad laminate having a thickness of 0.4 mm.
Table 4 shows the results of measurements of physical properties of
the copper-clad laminate.
Comparative Example 8
[0042] A copper-clad laminate having a thickness of 0.4 mm was
obtained in the same manner as in Example 4 except that 50 parts by
weight of 3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone used in
Example 4 was replaced with 50 parts by weight of a prepolymer of
2,2-bis(4-cyanatophenyl)propane (BT2070, supplied by Mitsubishi Gas
Chemical Company, Inc.). Table 4 shows the results of measurements
of physical properties of the copper-clad laminate.
Comparative Example 9
[0043] A copper-clad laminate having a thickness of 0.4 mm was
obtained in the same manner as in Example 4 except that 50 parts by
weight of 3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone used in
Example 4 was replaced with 50 parts by weight of a phenol novolak
type cyanate ester resin (Primaset PT-30, supplied by LONZA). Table
4 shows the results of measurements of physical properties of the
copper-clad laminate.
TABLE-US-00004 TABLE 4 (Table 4) Comparative Comparative Example 4
Example 8 Example 9 Glass transition 287 258 294 temperature Heat
resistance 1/4 2/4 3/4 after moisture absorption Burning V-0 Burnt
V-0 resistance
Example 5
[0044] 30 parts by weight of
3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone obtained in
Synthetic Example 1, 50 parts by weight of a biphenyl aralkyl type
epoxy resin (NC3000-H, supplied by Nippon Kayaku Co., Ltd.) and 20
parts by weight of bis(4-maleimidophenyl)methane (BMI-H, supplied
by K I KASEI KK) were dissolved in methyl ethyl ketone. Further,
100 parts by weight of a spherical synthetic silica (SC-2050,
supplied by ADMATECHS CO., LTD) and 0.04 part by weight of zinc
octylate were mixed with the resultant solution to obtain a
varnish. The varnish was diluted with methyl ethyl ketone. The
diluted varnish was impregnated into an E glass cloth having a
thickness of 0.1 mm. The impregnated varnish was dried under heat
at 165.degree. C. for 14 minutes, thereby obtaining prepregs. Four
prepregs obtained above were stacked and 12 .mu.m-thick
electrolytic copper foils were placed on the upper and lower
surfaces of the stack of the prepregs, one copper foil on the upper
surface and one copper foil on the lower surface, and the prepregs
and the copper foils were pressed at a pressure of 30 kgf/cm.sup.2
at a temperature of 220.degree. C. for 120 minutes, thereby
obtaining a copper-clad laminate having a thickness of 0.4 mm.
Table 5 shows the results of measurements of physical properties of
the copper-clad laminate.
Comparative Example 10
[0045] A copper-clad laminate having a thickness of 0.4 mm was
obtained in the same manner as in Example 5 except that 30 parts by
weight of 3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone used in
Example 5 was replaced with 30 parts by weight of a prepolymer of
2,2-bis(4-cyanatophenyl)propane (BT2070, supplied by Mitsubishi Gas
Chemical Company, Inc.). Table 5 shows the results of measurements
of physical properties of the copper-clad laminate.
Comparative Example 11
[0046] A copper-clad laminate having a thickness of 0.4 mm was
obtained in the same manner as in Example 5 except that 30 parts by
weight of 3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone used in
Example 5 was replaced with 30 parts by weight of a phenol novolak
type cyanate ester resin (Primaset PT-30, supplied by LONZA). Table
5 shows the results of measurements of physical properties of the
copper-clad laminate.
Example 6
[0047] 15 parts by weight of
3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone obtained in
Synthetic Example 1, 15 parts by weight of a phenol novolak type
cyanate ester resin (Primaset PT-30, supplied by LONZA), 50 parts
by weight of a biphenyl aralkyl type epoxy resin (NC3000-H,
supplied by Nippon Kayaku Co., Ltd.) and 20 parts by weight of
bis(4-maleimidophenyl)methane (BMI-H, supplied by K I KASEI KK)
were dissolved in methyl ethyl ketone. Further, 100 parts by weight
of a spherical synthetic silica (SC-2050, supplied by ADMATECHS
CO., LTD) and 0.06 part by weight of zinc octylate were mixed with
the resultant solution to obtain a varnish. The varnish was diluted
with methyl ethyl ketone. The diluted varnish was impregnated into
an E glass cloth having a thickness of 0.1 mm. The impregnated
varnish was dried under heat at 165.degree. C. for 5 minutes,
thereby obtaining prepregs. Four prepregs obtained above were
stacked and 12 .mu.m-thick electrolytic copper foils were placed on
the upper and lower surfaces of the stack of the prepregs, one
copper foil on the upper surface and one copper foil on the lower
surface, and the prepregs and the copper foils were pressed at a
pressure of 30 kgf/cm.sup.2 at a temperature of 220.degree. C. for
120 minutes, thereby obtaining a copper-clad laminate having a
thickness of 0.4 mm. Table 6 shows the results of measurements of
physical properties of the copper-clad laminate.
Comparative Example 12
[0048] A copper-clad laminate having a thickness of 0.4 mm was
obtained in the same manner as in Example 6 except that 15 parts by
weight of 3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone used in
Example 6 was replaced with 15 parts by weight of a prepolymer of
2,2-bis(4-cyanatophenyl)propane (BT2070, supplied by Mitsubishi Gas
Chemical Company, Inc.). Table 6 shows the results of measurements
of physical properties of the copper-clad laminate.
TABLE-US-00005 TABLE 5 (Table 5) Comparative Comparative Example 5
Example 10 Example 11 Glass transition 278 269 287 temperature
(.degree. C.) Heat resistance 0/4 0/4 2/4 after moisture absorption
Burning V-1 Burnt V-1 resistance
TABLE-US-00006 TABLE 6 (Table 6) Comparative Example 6 Example 12
Glass transition 282 275 temperature (.degree. C.) Heat resistance
after 0/4 2/4 moisture absorption Burning resistance V-1 Burnt
[0049] (Measurement Methods)
[0050] 1) Glass Transition Temperature (unit: .degree. C.)
[0051] Cast molded product: A specimen having a size of 5
mm.times.5 mm.times.3 mm was prepared. The specimen was measured
for a glass transition temperature with a TMA device (TA Instrument
type 2940) at a loading of 5 g at a temperature-increasing rate of
10.degree. C./min.
[0052] Laminate: Copper foils of a double-side copper-clad laminate
were completely removed. Then, the resultant laminate was measured
for a glass transition temperature by DMA method in conformity with
JIS-K6481.
[0053] 2) Bending Elastic Modulus (unit: GPa)
[0054] A specimen having a size of 10 mm.times.50 mm.times.2 mm was
prepared. The specimen was measured for a bending elastic modulus
with an autograph (supplied by SHIMADZU CORPORATION, AG5000B) at
normal temperature in conformity with JIS-K6911.
[0055] 3) Heat Resistance After Moisture Absorption
[0056] A copper-clad laminate sample having a size of 50
mm.times.50 mm was prepared. The entire copper foil of the sample
other than a copper foil on the half of one surface of the sample
was removed by etching, to prepare a specimen. The specimen was
treated with a pressure cooker testing machine (supplied by
Hirayama Manufacturing Corporation, PC-3 type) at 121.degree. C. at
2 atmospheric pressure for 3 hours or 5 hours. Then, the specimen
was immersed in solder at 260.degree. C. for 30 seconds. Then, an
appearance change was observed by visual observation (the number of
swelled specimens/the number of tested specimens).
[0057] 4) Burning Resistance
[0058] Measured in conformity with a UL 94 vertical test
method.
[0059] 5) Copper Foil Peeling Strength (unit: kgf/cm)
[0060] Measured in conformity with JIS-C6481.
* * * * *